JP3479648B2 - Polysilazane treatment solvent and method for treating polysilazane using this solvent - Google Patents

Polysilazane treatment solvent and method for treating polysilazane using this solvent

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Publication number
JP3479648B2
JP3479648B2 JP2001396328A JP2001396328A JP3479648B2 JP 3479648 B2 JP3479648 B2 JP 3479648B2 JP 2001396328 A JP2001396328 A JP 2001396328A JP 2001396328 A JP2001396328 A JP 2001396328A JP 3479648 B2 JP3479648 B2 JP 3479648B2
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JP
Japan
Prior art keywords
polysilazane
solvent
coating
film
coating film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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JP2001396328A
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Japanese (ja)
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JP2003197611A (en
Inventor
泰雄 清水
直 鈴木
Original Assignee
クラリアント インターナショナル リミテッド
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Priority to JP2001396328A priority Critical patent/JP3479648B2/en
Application filed by クラリアント インターナショナル リミテッド filed Critical クラリアント インターナショナル リミテッド
Priority to US10/499,374 priority patent/US7344603B2/en
Priority to EP02805890.7A priority patent/EP1463099B1/en
Priority to PCT/JP2002/013323 priority patent/WO2003056615A1/en
Priority to KR1020047010138A priority patent/KR100859276B1/en
Priority to CNB028259491A priority patent/CN100565814C/en
Priority to TW091137500A priority patent/TWI308576B/en
Publication of JP2003197611A publication Critical patent/JP2003197611A/en
Application granted granted Critical
Publication of JP3479648B2 publication Critical patent/JP3479648B2/en
Priority to US11/860,763 priority patent/US20080234163A1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041—Cleaning
    • H01L21/02082—Cleaning product to be cleaned
    • H01L21/02087—Cleaning of wafer edges
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/02—Chemical treatment or coating of shaped articles made of macromolecular substances with solvents, e.g. swelling agents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
    • H01L21/02208—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
    • H01L21/02219—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and nitrogen
    • H01L21/02222—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and nitrogen the compound being a silazane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/312—Organic layers, e.g. photoresist
    • H01L21/3121—Layers comprising organo-silicon compounds
    • H01L21/3125—Layers comprising organo-silicon compounds layers comprising silazane compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/16—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【発明の属する技術分野】本発明は、基材上に形成され
たポリシラザン塗膜またはポリシラザン被膜などを処理
する際に好適に用いられるポリシラザン処理溶剤および
この溶剤を用いてポリシラザンを処理する処理方法に関
する。TECHNICAL FIELD The present invention relates to a polysilazane treatment solvent which is preferably used when treating a polysilazane coating film or a polysilazane coating film formed on a substrate, and a treatment method for treating polysilazane using this solvent. .

【０００２】[0002]

【従来の技術】従来、シリカ質の膜を絶縁膜、誘電体
膜、保護膜あるいは親水化膜などとして利用することは
広く知られている。このようなシリカ質の膜を基材上に
形成する方法としては、ＰＶＤ法（スパッタ法等）ＣＶ
Ｄ法、ゾルゲル法、およびポリシロキサンあるいはポリ
シラザン塗膜を形成し、この塗膜を焼成などによりシリ
カ質の膜に転化する方法など種々の方法が用いられてい
る。これらの方法のうちＰＶＤ法、ＣＶＤ法は装置が高
価であるとともに、良質な塗膜を形成するための制御が
煩雑であるという問題がある。またゾル−ゲル法では、
必要焼成温度が５００℃以上と高いという問題がある。
さらに、ポリシロキサンを用いる方法は、形成された被
膜の膜厚減少などによるクラックの発生などの問題があ
る。これに対し、ポリシラザン溶液を塗布し、この塗膜
をシリカ質の膜に転化する方法は、低温焼成により優れ
た特性を有するシリカ質膜を簡便に形成することができ
るとともに、形成されたシリカ質被膜の膜質も優れてい
ることから、近年特に注目されている。2. Description of the Related Art Conventionally, it is widely known that a siliceous film is used as an insulating film, a dielectric film, a protective film, a hydrophilic film or the like. As a method for forming such a siliceous film on a substrate, PVD method (sputtering method, etc.) CV
Various methods such as the D method, the sol-gel method, and the method of forming a polysiloxane or polysilazane coating film and converting the coating film into a siliceous film by firing or the like are used. Among these methods, the PVD method and the CVD method have problems that the apparatus is expensive and that control for forming a high quality coating film is complicated. In the sol-gel method,
There is a problem that the required firing temperature is as high as 500 ° C or higher.
Further, the method using polysiloxane has a problem such as generation of cracks due to a decrease in film thickness of the formed coating film. On the other hand, a method of applying a polysilazane solution and converting this coating film into a siliceous film can easily form a siliceous film having excellent properties by low-temperature firing, and the formed siliceous film Since the film quality of the film is also excellent, it has been particularly noted in recent years.

【０００３】このようなシリカ質の膜は、例えばＬＳ
Ｉ、ＴＦＴ液晶表示装置などの半導体素子の層間絶縁
膜、平坦化膜、パシベーション膜、素子間分離絶縁体な
どとして広く利用されている。このようなシリカ質の膜
を半導体素子等に形成する場合、通常次のような方法が
採られている。すなわち、まず、必要に応じ半導体、配
線、電極等が形成された、段差を有するあるいは段差を
有さない基板上にポリシラザン溶液をスピンコートし、
加熱して塗膜から溶剤が除去され、次いで、３５０℃以
上の温度で焼成してポリシラザンがシリカ質の膜に転化
され、この添加されたシリカ質の膜が層間絶縁膜、平坦
化膜、パシベーション膜、素子間分離絶縁体などとし利
用されている。しかし、このような方法においては、ポ
リシラザン溶液を基板上にスピンコートした際に、基板
の周縁にビードが形成されるとともに、基板裏面に溶液
が周り込むことは広く知られている。このビードによる
基板周縁部での塗膜の膜厚の不均一化を防ぐため、通常
ポリシラザン溶液を塗布してポリシラザン膜を形成する
際にエッジリンスが行われ、またこれとともに基板裏面
に周り込んで付着したポリシラザンを除去し裏面を清浄
にするため、バックリンスが行われる。Such a siliceous film is, for example, LS
I, widely used as an interlayer insulating film, a flattening film, a passivation film, an element isolation insulator, etc. of a semiconductor element such as a TFT liquid crystal display device. When forming such a siliceous film on a semiconductor device or the like, the following method is usually adopted. That is, first, a polysilazane solution is spin-coated on a substrate having semiconductors, wirings, electrodes, etc., which have steps or steps, if necessary.
The solvent is removed from the coating by heating, and then the polysilazane is converted into a siliceous film by baking at a temperature of 350 ° C. or higher. The added siliceous film is an interlayer insulating film, a planarizing film, and a passivation film. It is used as a film and element isolation insulator. However, in such a method, it is widely known that when the polysilazane solution is spin-coated on the substrate, a bead is formed on the periphery of the substrate and the solution surrounds the back surface of the substrate. In order to prevent nonuniformity of the film thickness of the coating film at the peripheral edge of the substrate due to this bead, edge rinse is usually performed when the polysilazane solution is applied to form the polysilazane film. A back rinse is performed to remove the attached polysilazane and clean the back surface.

【０００４】また、このような方法で塗布して形成され
たポリシラザン被膜を基板から剥離することが必要とさ
れる場合もあるし、またスピンコーターなどの塗布装置
に付着したポリシラザンを洗浄、除去することも必要と
される。In some cases, it is necessary to peel off the polysilazane film formed by coating by such a method from the substrate, and the polysilazane adhering to a coating device such as a spin coater is washed and removed. Things are also needed.

【０００５】従来、このようなポリシラザンを除去する
ためのリンス液あるいは剥離液として、例えばプロピレ
ングリコールモノメチルエーテルアセテート（ＰＧＭＥ
Ａ）等を用いることが知られている。しかし、これら公
知のリンス液あるいは剥離液によるとポリシラザンのリ
ンスあるいは剥離が十分に行えないとか、ポリシラザン
のリンスあるいは剥離は十分に行えるものの、廃液のゲ
ル化に伴うスピンコーター等の塗布装置の廃液ラインの
閉塞あるいは廃液タンク中でのシラン、水素、アンモニ
ア等のガスの発生の問題などが起こることがある。廃液
のゲル化が起こるような場合には、塗布装置および廃液
ラインの洗浄作業を頻繁に行う必要があるし、またシラ
ンガス等が廃液タンクで発生し、シランの濃度が自然発
火限界を超えるような場合には、廃液タンクの蓋を開け
た瞬間に爆発が起こるなど大変危険な状態となる。Conventionally, for example, propylene glycol monomethyl ether acetate (PGME) has been used as a rinse solution or a stripping solution for removing such polysilazane.
It is known to use A) or the like. However, according to these known rinse liquids or stripping solutions, the polysilazane cannot be rinsed or stripped sufficiently, or the polysilazane can be rinsed or stripped sufficiently, but the waste liquid line of a coating device such as a spin coater accompanying the gelation of the waste liquid. There may be a problem such as clogging of the tank or generation of gas such as silane, hydrogen and ammonia in the waste liquid tank. When the waste liquid gels, it is necessary to frequently clean the coating device and the waste liquid line, and silane gas etc. is generated in the waste liquid tank, and the concentration of silane exceeds the spontaneous ignition limit. In this case, it becomes a very dangerous state such as an explosion at the moment the lid of the waste liquid tank is opened.

【０００６】また、ポリシラザン塗膜から形成されたシ
リカ質の膜は、半導体素子以外にも、液晶表示装置、プ
ラズマディスプレイパネル（ＰＤＰ）などの誘電体膜、
絶縁膜あるいは隔壁膜などとして、さらには自動車など
の車体表面、住宅の内外装、ガラス製品、陶磁器、プラ
スチック製品などの各種物品の保護被膜などとして種々
の分野で用いられており、これら分野でも半導体素子の
製造における場合と同様、不要部に付着したポリシラザ
ン被膜を除去しなくてはならないという問題が生じる場
合がある。The siliceous film formed from the polysilazane coating film is used for a dielectric film of a liquid crystal display device, a plasma display panel (PDP), etc. in addition to the semiconductor element.
It is used in various fields as an insulating film or partition film, and as a protective film for various surfaces such as car body surfaces of automobiles, interiors and exteriors of houses, glass products, ceramics, plastic products, etc. As in the case of manufacturing the device, there may be a problem that the polysilazane film attached to the unnecessary portion must be removed.

【０００７】[0007]

【発明が解決しようとする課題】本発明は、ポリシラザ
ン塗膜あるいはポリシラザン被膜などのリンス、剥離な
どの際に上記したような問題点のないポリシラザン処理
溶剤およびこれを用いるポリシラザンの処理方法を提供
することを目的とするものである。DISCLOSURE OF THE INVENTION The present invention provides a polysilazane treatment solvent which does not have the above-mentioned problems when rinsing or peeling a polysilazane coating film or a polysilazane coating film, and a polysilazane treatment method using the same. That is the purpose.

【０００８】すなわち、本発明は、ポリシラザンの溶解
性に優れ、下地となる半導体あるいは基板などの特性お
よび残留するポリシラザン塗膜の特性に影響を与えるこ
とのないポリシラザン処理溶剤およびこの溶剤を用いて
ポリシラザンを処理する方法を提供することを目的とす
る。That is, the present invention provides a polysilazane treatment solvent which is excellent in the solubility of polysilazane and does not affect the characteristics of the underlying semiconductor or substrate and the characteristics of the remaining polysilazane coating film, and the polysilazane using this solvent. The purpose is to provide a method of handling.

【０００９】また、本発明は、上記特性に加えポリシラ
ザン塗膜に対するエッジカット性に優れ、ポリシラザン
の分解性を殆ど有さないポリシラザン処理溶剤およびこ
の溶剤を用いてポリシラザンを処理する方法を提供する
ことを目的とする。Further, the present invention provides a polysilazane treatment solvent which is excellent in edge-cutting property for a polysilazane coating film in addition to the above-mentioned properties and has almost no decomposability of polysilazane, and a method for treating polysilazane using this solvent. With the goal.

【００１０】[0010]

【課題を解決するための手段】本発明者は、このような
課題を解決すべく鋭意研究、検討を重ねた結果、ポリシ
ラザンのリンス液、剥離液を含む処理液には、ポリシラ
ザンを良好に溶解でき、またエッジカット性が良好であ
るという特性が要求されることは言うに及ばず、さらに
下地の特性、形成されるシリカ質の膜特性に影響を与え
ないようにするため、溶剤中のパーティクルが少なく、
金属不純物が少ないことが必要であり、また廃液ライン
の詰まりや廃液タンク中でのシランガス等の発生を防止
するには、溶剤自体ポリシラザンを分解する基（水酸
基、エステル基など）を含まず、水分を吸収し難いとい
う特性が要求されることを見い出し、本発明をなしたも
のである。Means for Solving the Problems As a result of intensive studies and studies for solving the above problems, the present inventor has found that polysilazane is satisfactorily dissolved in a treatment solution containing a rinse solution and a stripping solution of polysilazane. Needless to say, it is required to have the property that it can be formed and has good edge-cutting property. In addition, in order not to affect the properties of the underlayer and the properties of the formed siliceous film, the particles in the solvent Is less
It is necessary that the metal impurities have small, and to prevent the occurrence of the silane gas or the like in the clogging or waste tank in the waste line is free of decomposing the solvent itself polysilazane group (hydroxyl group, such as an ester group), The present invention has been made by discovering that the characteristic that it is difficult to absorb water is required.

【００１１】すなわち、本発明は、キシレン、アニソー
ル、デカリン、シクロヘキサン、シクロヘキセン、メチ
ルシクロヘキサン、エチルシクロヘキサン、リモネン、
ヘキサン、オクタン、ノナン、デカン、Ｃ８−Ｃ１１ア
ルカン混合物、Ｃ８−Ｃ１１芳香族炭化水素混合物、Ｃ
８以上の芳香族炭化水素を５重量％以上、２５重量％以
下含有する脂肪族／脂環式炭化水素混合物、およびジブ
チルエーテルからなる群から選ばれる一種または二種以
上からなる単一または混合溶剤であって、該溶剤の１ｍ
ｌ中に含まれる０．５ミクロン以上の微粒子が５０個以
下であり、また水分含有率が１００ｐｐｍ以下であるこ
とを特徴とするポリシラザン塗膜または被膜のリンスま
たは剥離用処理溶剤を提供するものである。That is, the present invention relates to xylene, anisole, decalin, cyclohexane, cyclohexene, methylcyclohexane, ethylcyclohexane, limonene,
Hexane, octane, nonane, decane, C8-C11 alkane mixture, C8-C11 aromatic hydrocarbon mixture, C
Aliphatic / alicyclic hydrocarbon mixture containing 8 or more aromatic hydrocarbons in an amount of 5% by weight or more and 25% by weight or less, and a single or mixed solvent consisting of one or more selected from the group consisting of dibutyl ether. And 1m of the solvent
A polysilazane coating film or a rinse film containing 50 or less fine particles of 0.5 micron or more and a water content of 100 ppm or less.
Or to provide a stripping treatment solvent.

【００１２】また、本発明は、キシレン、Ｃ８−Ｃ１１
芳香族炭化水素混合物またはＣ８以上の芳香族炭化水素
を５重量％以上、２５重量％以下含有する脂肪族／脂環
式炭化水素混合物を５０重量％以上含有する混合溶剤で
ある上記ポリシラザン塗膜または被膜のリンスまたは剥
離用処理溶剤を提供するものである。The present invention also provides xylene, C8-C11.
The above polysilazane coating film which is an aromatic hydrocarbon mixture or a mixed solvent containing 50% by weight or more of an aliphatic / alicyclic hydrocarbon mixture containing 5% by weight or more and 25% by weight or less of C8 or more aromatic hydrocarbons or Rinse or strip coating
A release treatment solvent is provided.

【００１３】さらに、本発明は、上記ポリシラザン塗膜
または被膜のリンスまたは剥離用処理溶剤に、さらに希
釈溶剤としてミネラルスピリットが含有されることを特
徴とするポリシラザン塗膜または被膜のリンスまたは剥
離用処理溶剤。Furthermore, the present invention provides the above polysilazane coating film.
Alternatively, the treatment solvent for rinsing or peeling the coating further contains mineral spirit as a diluting solvent, and the rinsing or peeling of the polysilazane coating or coating is performed.
Release treatment solvent.

【００１４】[0014]

【００１５】また、本発明は、上記各処理溶剤の処理対
象となるポリシラザンが、ペルヒドロポリシラザン、メ
タノール付加ペルヒドロポリシラザンまたはヘキサメチ
ルジシラザン付加ペルヒドロポリシラザンであることを
特徴とするポリシラザン塗膜または被膜のリンスまたは
剥離用処理溶剤を提供するものである。Further, the present invention is polysilazane to be processed by the above processes solvent, perhydropolysilazane, polysilazane coating or being a methanol addition perhydropolysilazane or hexamethyldisilazane added perhydropolysilazane Coating rinse or
A treatment solvent for peeling is provided.

【００１６】また、本発明は、上記各処理溶剤をポリシ
ラザンと接触させることを特徴とするポリシラザン塗膜
または被膜のリンスまたは剥離処理方法を提供するもの
である。Further, according to the present invention, the polysilazane coating film is characterized in that each of the above processing solvents is brought into contact with polysilazane.
Alternatively, the present invention provides a method for rinsing or peeling a coating film .

【００１７】また、本発明は、上記ポリシラザン塗膜ま
たは被膜のリンスまたは剥離処理方法において、上記各
処理溶剤のポリシラザンとの接触が、ポリシラザン溶液
を基板に塗布した後、前記処理溶剤を基板のポリシラザ
ン塗布面のエッジ部または裏面に噴射することによりな
されることを特徴とするポリシラザン塗膜または被膜の
リンスまたは剥離処理方法を提供するものである。The present invention also provides the above polysilazane coating film.
In addition, in the method of rinsing or peeling the coating,
Contact with the polysilazane processing solvent, after application of the polysilazane solution to the substrate, the polysilazane coating film or coating characterized in that it is made by injecting the treating solvent the edge portion or the back of the polysilazane coating surface of the substrate
A method for rinsing or peeling treatment is provided.

【００１８】以下、本発明を更に詳細に説明する。本発
明においては、溶剤として、キシレン、アニソール、デ
カリン、シクロヘキサン、シクロヘキセン、メチルシク
ロヘキサン、エチルシクロヘキサン、リモネン、ヘキサ
ン、オクタン、ノナン、デカン、Ｃ８−Ｃ１１アルカン
混合物、Ｃ８−Ｃ１１芳香族炭化水素混合物、例えばソ
ルベッソ１００あるいはソルベッソ１５０（エクソンモ
ービル社）、Ｃ８以上の芳香族炭化水素を５重量％以
上、２５重量％以下含有する脂肪族／脂環式炭化水素混
合物、例えばペガソールＡＮ４５（エクソンモービル
社）、ジブチルエーテルからなる群から選ばれる一種ま
たは二種以上からなる単一または混合溶剤が用いられ
る。これら溶剤の１ｍｌ中に含まれる０．５ミクロン以
上の微粒子は、５０個以下であることが必要であるが、
１０個以下が好ましい。溶剤１ｍｌ中の０．５ミクロン
以上の微粒子の含有数が５０個を超える場合には、濾
過、蒸留など適宜の手段により溶剤中の微粒子を除去
し、溶剤１ｍｌ中に含まれる０．５ミクロン以上の微粒
子の数が５０個以下となるよう処理すればよい。溶剤１
ｍｌ中に含まれる０．５ミクロン以上の微粒子の数が５
０個を超える場合、処理されたポリシラザン膜中に微粒
子が残留することが間々みられ、このような場合にはポ
リシラザン膜を焼成してシリカ質の膜を形成した際に、
絶縁特性、誘電特性などの低下が見られることがあり、
またポリシラザンが塗布された半導体基板などに微粒子
が付着し、半導体特性や場合によっては短絡や導通不良
等によるデバイス収率の低下などの問題が発生すること
があるからである。この絶縁特性、誘電特性、半導体特
性、短絡の問題は、特に微粒子が金属である場合に往々
見られるため、金属微粒子についてはゼロとすることが
望ましい。さらに、０．２μｍ以上の粒子も４００個以
下であることがより望ましい。The present invention will be described in more detail below. In the present invention, as the solvent, xylene, anisole, decalin, cyclohexane, cyclohexene, methylcyclohexane, ethylcyclohexane, limonene, hexane, octane, nonane, decane, a C8-C11 alkane mixture, a C8-C11 aromatic hydrocarbon mixture, for example, Solvesso 100 or Solvesso 150 (ExxonMobil), an aliphatic / alicyclic hydrocarbon mixture containing 5% by weight or more and 25% by weight or less of C8 or more aromatic hydrocarbon, such as Pegasol AN45 (ExxonMobil), Di A single or mixed solvent consisting of one or more selected from the group consisting of butyl ether is used. It is necessary that the number of fine particles of 0.5 micron or more contained in 1 ml of these solvents is 50 or less.
It is preferably 10 or less. When the content of fine particles of 0.5 micron or more in 1 ml of solvent exceeds 50, the fine particles in the solvent are removed by an appropriate means such as filtration or distillation, and 0.5 micron or more contained in 1 ml of the solvent. The number of fine particles may be reduced to 50 or less. Solvent 1
The number of fine particles of 0.5 micron or more contained in ml is 5
When the number exceeds 0, it is often observed that fine particles remain in the treated polysilazane film. In such a case, when the polysilazane film is baked to form a siliceous film,
Insulation characteristics and dielectric characteristics may deteriorate.
Further, fine particles may adhere to a semiconductor substrate or the like coated with polysilazane, which may cause a problem such as a decrease in device yield due to semiconductor characteristics or, in some cases, a short circuit or conduction failure. Since the problems of the insulating property, the dielectric property, the semiconductor property, and the short circuit are often seen especially when the fine particles are made of metal, it is desirable to set the fine metal particles to zero. Further, it is more desirable that the number of particles of 0.2 μm or more is 400 or less.

【００１９】上記本発明の溶剤はいずれもポリシラザン
の溶解性が優れている。このため、例えば芳香族系の炭
化水素を用いる場合には、単一溶剤としてではなく、上
記溶剤のうちの脂肪族系炭化水素、脂環式系炭化水素あ
るいはジブチルエーテルとともに混合溶剤として用いる
ことができる。すなわち、溶剤として芳香族系炭化水素
溶剤であるキシレン、Ｃ８−Ｃ１１芳香族炭化水素混合
物（例えばソルベッソ１００、ソルベッソ１５０）、あ
るいはＣ８以上の芳香族炭化水素を５重量％以上、２５
重量％以下含有する脂肪族／脂環式炭化水素混合物（例
えばペガソールＡＮ４５）などを用いる場合には、脂肪
族系炭化水素、脂環式系炭化水素である、例えばシクロ
ヘキサン、ノナンなどとの混合溶剤とすることができ
る。このとき、芳香族系の炭化水素の量が溶剤中１０重
量％程度以上であれば、通常溶解性を高めることができ
る。ポリシラザンに対する溶解性の点からみれば、芳香
族系溶剤の含有量が多いものが好ましいが、特に、キシ
レン、Ｃ８−Ｃ１１芳香族炭化水素混合物（例えばソル
ベッソ１００、ソルベッソ１５０）またはＣ８以上の芳
香族炭化水素を５重量％以上、２５重量％以下含有する
脂肪族／脂環式炭化水素混合物（例えばペガソールＡＮ
４５）を５０重量％以上含有する溶剤は、ペルヒドロポ
リシラザン、メタノール付加ペルヒドロポリシラザンお
よびヘキサメチルジシラザン付加ペルヒドロポリシラザ
ンのいずれに対しても溶解性が良好で、エッジカット性
も優れており、また安価であるという点からポリシラザ
ン処理溶剤として特に好ましいものである。また、本発
明で用いられる溶剤は、本発明の目的が達成できる範囲
で、希釈溶剤としてミネラルスピリットを用いて希釈さ
れてもよい。なお、このとき使用されるミネラルスピリ
ットの１ｍｌ中に含まれる０．５ミクロン以上の微粒子
の数も５０個以下であることが必要である。さらに、メ
チルシクロヘキサン、エチルシクロヘキサンなどは臭い
が少ないので、無臭性が要求される場合には、このよう
な臭いの少ない溶剤を選択すればよい。なお、ぺガソー
ルＡＮ４５は、原油の常圧蒸留で得られる流出油を水素
化精製した留分で、主にＣ８〜Ｃ１１の範囲の石油系炭
化水素であり、アニリン点が４３℃の液体である。Each of the above-mentioned solvents of the present invention has excellent solubility in polysilazane. Therefore, for example, when aromatic hydrocarbons are used, they should not be used as a single solvent but as a mixed solvent with an aliphatic hydrocarbon, an alicyclic hydrocarbon or dibutyl ether among the above solvents. it can. That is, xylene, which is an aromatic hydrocarbon solvent, a C8-C11 aromatic hydrocarbon mixture (for example, Solvesso 100, Solvesso 150), or an aromatic hydrocarbon having a C8 or more of 5% by weight or more, 25
When using an aliphatic / alicyclic hydrocarbon mixture (eg, Pegasol AN45) containing less than or equal to wt%, a mixed solvent with an aliphatic hydrocarbon or an alicyclic hydrocarbon such as cyclohexane or nonane Can be At this time, if the amount of the aromatic hydrocarbon is about 10% by weight or more in the solvent, the solubility can be usually increased. From the viewpoint of solubility in polysilazane, it is preferable that the content of the aromatic solvent is large, but in particular, xylene, a C8-C11 aromatic hydrocarbon mixture (for example, Solvesso 100, Solvesso 150) or a C8 or higher aromatic solvent. Aliphatic / alicyclic hydrocarbon mixture containing 5% by weight or more and 25% by weight or less of hydrocarbon (for example, Pegasol AN
A solvent containing 45% by weight or more of 45) has good solubility in any of perhydropolysilazane, methanol-added perhydropolysilazane and hexamethyldisilazane-added perhydropolysilazane, and has excellent edge-cutting property, Further, it is particularly preferable as a polysilazane treatment solvent because it is inexpensive. Further, the solvent used in the present invention may be diluted with mineral spirit as a diluting solvent within the range in which the object of the present invention can be achieved. The number of fine particles of 0.5 micron or more contained in 1 ml of the mineral spirit used at this time must be 50 or less. Further, since methylcyclohexane, ethylcyclohexane, and the like have a small odor, when odorlessness is required, a solvent having such a small odor may be selected. Pegasol AN45 is a fraction obtained by hydrorefining the spilled oil obtained by atmospheric distillation of crude oil, which is a petroleum hydrocarbon mainly in the range of C8 to C11 and a liquid having an aniline point of 43 ° C. .

【００２０】また、本発明の溶剤は、水分含有率が１０
０ｐｐｍ以下であることが好ましく、８０ｐｐｍ以下が
より好ましい。水分含有量が１００ｐｐｍを超えると、
溶剤と接触するポリシラザンの分解によるゲル化が早期
に起るようになり、例えば、スピンコーターの廃液ライ
ンの閉塞、スピンコーターなどに付着したポリシラザン
の除去に時間がかかるなどの問題が発生するようになる
ため好ましくない。また廃液タンク中で基板から除去さ
れたポリシラザンが水分と接触することにより、シラ
ン、水素、アンモニア等のガスが発生し、シランの濃度
が自然発火限界を超えるようなことがあると、前記した
ように最悪の場合には廃液タンクの爆発にも結び付く恐
れがある。The solvent of the present invention has a water content of 10
It is preferably 0 ppm or less, and more preferably 80 ppm or less. If the water content exceeds 100 ppm,
Gelation due to decomposition of polysilazane in contact with a solvent will occur early, for example, a problem such as clogging of a waste liquid line of a spin coater, removal of polysilazane adhering to a spin coater, etc. will occur. Is not preferable. In addition, when the polysilazane removed from the substrate in the waste liquid tank comes into contact with water, gas such as silane, hydrogen, and ammonia is generated, and the concentration of silane may exceed the spontaneous ignition limit, as described above. In the worst case, it may lead to the explosion of the waste liquid tank.

【００２１】また、前記単一溶剤あるいは混合溶剤とし
てどのようなものが好ましいかは、処理対象となるポリ
シラザンがどのような構造、あるいは組成のものである
かによる。すなわち、ポリシラザンの溶解性は、溶剤と
して同じものが用いられたとしても、ポリシラザンが無
機のポリシラザンであるか、有機のポリシラザンである
か、単一重合体か共重合体か、共重合体であれば共重合
されたものがなにか、重合体中に環状構造を有するか有
しないか、ポリシラザンが更に化学的に変性されている
かどうか、添加剤が別途加えられているかどうかなど種
々の条件により異なるし、また、同じポリシラザンに対
する溶解性も溶剤により異なるからである。したがっ
て、処理されるポリシラザンの構造、あるいは組成に応
じ上記本発明の溶剤から適宜最適のものを選択するよう
にすればよい。What is preferable as the single solvent or mixed solvent depends on the structure or composition of the polysilazane to be treated. That is, the solubility of the polysilazane, even if the same solvent is used, polysilazane is an inorganic polysilazane, an organic polysilazane, a homopolymer or a copolymer, if the copolymer What is copolymerized, whether or not it has a cyclic structure in the polymer, whether the polysilazane is further chemically modified, it depends on various conditions such as whether additives are added separately, depending on various conditions, Also, the solubility for the same polysilazane differs depending on the solvent. Therefore, the most suitable solvent may be selected from the above solvents of the present invention depending on the structure or composition of the polysilazane to be treated.

【００２２】一方、本発明の溶剤が適用されるポリシラ
ザンは、無機あるいは有機のいずれのものであってもよ
い。これらポリシラザンのうち、無機ポリシラザンとし
ては、例えば一般式：On the other hand, the polysilazane to which the solvent of the present invention is applied may be either inorganic or organic. Among these polysilazanes, examples of the inorganic polysilazane include those represented by the general formula:

【００２３】[0023]

【化１】 [Chemical 1]

【００２４】で示される構造単位を有する直鎖状構造を
包含し、６９０〜２０００の分子量を持ち、一分子中に
３〜１０個のＳｉＨ3基を有し、化学分析による元素比
率がＳｉ：５９〜６１、Ｎ：３１〜３４およびＨ：６．
５〜７．５の各重量％であるペルヒドロポリシラザン
（特公昭６３−１６３２５号公報）、およびポリスチレ
ン換算平均分子量が３，０００〜２０，０００の範囲に
あるペルヒドロポリシラザンが挙げられる。It includes a linear structure having a structural unit represented by the formula (1), has a molecular weight of 690 to 2000, has 3 to 10 SiH 3 groups in one molecule, and has an element ratio of Si by chemical analysis: 59-61, N: 31-34 and H: 6.
Examples include perhydropolysilazane (Japanese Patent Publication No. 63-16325) in which each weight% is 5 to 7.5, and perhydropolysilazane having a polystyrene-converted average molecular weight in the range of 3,000 to 20,000.

【００２５】これらペルヒドロポリシラザンは、上記特
公昭６３−１６３２５号公報に記載された方法あるいは
Ｄ．Ｓｅｙｆｅｒｔｈら、Ｃｏｍｍｕｎｉｃａｔｉｏｎ
ｏｆ Ａｍ．Ｃｅｒ．Ｓｏｃ．，Ｃ−１３，Ｊａｎｕ
ａｒｙ １９８３などに報告されている方法により製造
することができ、基本的には分子内に鎖状部分と環状部
分を含むもので、These perhydropolysilazanes can be prepared by the method described in Japanese Patent Publication No. 63-16325 or D. Seeferth et al., Communication
of Am. Cer. Soc. , C-13, Janu
It can be produced by the method reported in ary 1983 and the like, and basically contains a chain portion and a cyclic portion in the molecule,

【００２６】[0026]

【化２】 [Chemical 2]

【００２７】の化学式で表すことができるものである。
ペルヒドロポリシラザン構造の一例を示すと下記のごと
くである。It can be represented by the chemical formula:
An example of the perhydropolysilazane structure is shown below.

【００２８】[0028]

【化３】 [Chemical 3]

【００２９】これらペルヒドロポリシラザンを処理する
ために適した溶剤としては、キシレン、アニソール、デ
カリン、シクロヘキサン、シクロヘキセン、メチルシク
ロヘキサン、エチルシクロヘキサン、リモネン、Ｃ８−
Ｃ１１芳香族炭化水素混合物、およびＣ８以上の芳香族
炭化水素を５重量％以上、２５重量％以下含有するパラ
フィン／シクロパラフィン炭化水素混合物、ジブチルエ
ーテルからなる群から選ばれる１種または二種以上から
なる単一または混合溶剤であって、該溶剤の１ｍｌ中に
含まれる０．５ミクロン以上の微粒子が５０個以下であ
る溶剤、より好ましくはさらに水分含有率が１００ｐｐ
ｍ以下である溶剤が挙げられる。また、これらの溶剤
は、必要に応じミネラルスピリットにより希釈されて用
いられてもよい。 Suitable solvents for treating these perhydropolysilazanes include xylene, anisole, decalin, cyclohexane, cyclohexene, methylcyclohexane, ethylcyclohexane, limonene, C8-.
C11 aromatic hydrocarbon mixture, and one or more selected from the group consisting of paraffin / cycloparaffin hydrocarbon mixture containing 5% by weight or more and 25% by weight or less of C8 or more aromatic hydrocarbon, dibutyl ether. Which is a single or mixed solvent having 50 or less fine particles of 0.5 micron or more contained in 1 ml of the solvent, and more preferably a water content of 100 pp.
Examples of the solvent include m or less. Further, these solvents may be used after being diluted with mineral spirits, if necessary.

【００３０】また、他のポリシラザンの例として、例え
ば、主として一般式：Examples of other polysilazanes include, for example, the general formula:

【化４】 [Chemical 4]

【００３１】（式中、Ｒ1、Ｒ2およびＲ3は、それぞれ
独立に水素原子、アルキル基、アルケニル基、シクロア
ルキル基、アリール基、もしくはこれらの基以外でフル
オロアルキル基等のケイ素に直結する基が炭素である
基、アルキルシリル基、アルキルアミノ基またはアルコ
キシ基を表す。但し、Ｒ1、Ｒ2およびＲ3の少なくとも
１つは水素原子である。）で表される構造単位からなる
骨格を有する数平均分子量が約１００〜５０，０００の
ポリシラザンまたはその変性物が挙げられる。(In the formula, R 1 , R 2 and R 3 are each independently a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or other than these groups, directly bonded to silicon such as a fluoroalkyl group. Represents a group having a carbon atom, an alkylsilyl group, an alkylamino group or an alkoxy group, provided that at least one of R 1 , R 2 and R 3 is a hydrogen atom). Examples thereof include polysilazanes having a skeleton and a number average molecular weight of about 100 to 50,000 or modified products thereof.

【００３２】例えば、上記一般式（II）でＲ1およびＲ2
に水素原子、Ｒ3にメチル基を有するポリシラザンの製
造方法は、Ｄ．ＳｅｙｆｅｒｔｈらＰｏｌｙｍ．Ｐｒｅ
ｐｒ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．，Ｄｉｖ．Ｐｏｌｙ
ｍ．Ｃｈｅｍ，．２５，１０（１９８４）に報告されて
いる。この方法により得られるポリシラザンは、繰り返
し単位が−（ＳｉＨ2ＮＣＨ3）−の鎖状ポリマーと環状
ポリマーであり、いずれも架橋構造をもたない。For example, in the above general formula (II), R 1 and R 2
A method for producing a polysilazane having a hydrogen atom in R and a methyl group in R 3 is described in D. Seeferth et al., Polym. Pre
pr. Am. Chem. Soc. , Div. Poly
m. Chem ,. 25, 10 (1984). The polysilazane obtained by this method is a chain polymer having a repeating unit of — (SiH 2 NCH 3 ) — and a cyclic polymer, and neither has a crosslinked structure.

【００３３】また、上記一般式（II）でＲ1およびＲ2に
水素原子、Ｒ3に有機基を有するポリオルガノ（ヒド
ロ）シラザンの製造法は、Ｄ．ＳｅｙｆｅｒｔｈらＰｏ
ｌｙｍ．Ｐｒｅｐｒ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．，Ｄｉ
ｖ．Ｐｏｌｙｍ．Ｃｈｅｍ，．２５，１０（１９８
４）、特開昭６１−８９２３０号公報に報告されてい
る。これら方法により得られるポリシラザンには、−
（Ｒ2ＳｉＨＮＨ）−を繰り返し単位として、主として
重合度が３〜５の環状構造を有するものや（Ｒ3ＳｉＨ
ＮＨ)x〔（Ｒ2ＳｉＨ）1.5Ｎ〕1-X（０．４＜Ｘ＜１）
の化学式で示される分子内に鎖状構造と環状構造を同時
に有するものがある。The method for producing polyorgano (hydro) silazane having hydrogen atoms in R 1 and R 2 and an organic group in R 3 in the general formula (II) is described in D. Seeferth et al Po
lym. Prepr. Am. Chem. Soc. , Di
v. Polym. Chem ,. 25, 10 (198
4), JP-A-61-89230. Polysilazanes obtained by these methods include-
(R 2 SiHNH) - as a repeating unit, and which mainly polymerization degree having a cyclic structure 3 to 5 (R 3 SiH
NH) x [(R 2 SiH) 1.5 N] 1-X (0.4 <X <1)
There is a compound having a chain structure and a cyclic structure simultaneously in the molecule represented by the chemical formula.

【００３４】さらに、上記一般式（II）でＲ1に水素原
子、Ｒ2、Ｒ3に有機基を有するポリシラザン、またＲ1
およびＲ2に有機基、Ｒ3に水素原子を有するものは−
（Ｒ1Ｒ 2ＳｉＮＲ3）−を繰り返し単位として、主に重
合度が３〜５の環状構造を有しているものもある。Further, in the above general formula (II), R1Hydrogen source
Child, R2, R3A polysilazane having an organic group in R, and R1
And R2Organic group, R3Those having a hydrogen atom in
(R1R 2SiNR3)-Is the main repeating unit.
Some have a ring structure with a degree of conformity of 3-5.

【００３５】また、上記一般式（II）以外の有機ポリシ
ラザンとしては、例えば一般式：Examples of the organic polysilazane other than the above general formula (II) include, for example, the general formula:

【化５】 [Chemical 5]

【００３６】で表わされる架橋構造を分子内に有するポ
リオルガノ（ヒドロ）シラザン（Ｄ．Ｓｅｙｆｅｒｔｈ
らＣｏｍｍｕｎｉｃａｔｉｏｎ ｏｆ Ａｍ．Ｃｅｒ．Ｓ
ｏｃ．Ｃ−１３２，Ｊｕｌｙ １９８４）、Ｒ1ＳｉＸ3
（Ｘ：ハロゲン）のアンモニア分解によって得られる架
橋構造を有するポリシラザンＲ1Ｓｉ（ＮＨ)x、あるい
はＲ1ＳｉＸ3およびＲ2 2ＳｉＸ2の共アンモニア分解に
よって得られる、下記の構造を有するポリシラザン（特
開昭４９−６９７１７号公報）が挙げられる。A polyorgano (hydro) silazane (D. Seyferth) having a crosslinked structure represented by
Communication of Am. Cer. S
oc. C-132, July 1984), R 1 SiX 3
A crosslinked polysilazane R 1 Si (NH) x obtained by ammonia decomposition of (X: halogen) or a polysilazane having the following structure obtained by co-ammonia decomposition of R 1 SiX 3 and R 2 2 SiX 2 ( JP-A-49-69717).

【００３７】[0037]

【化６】 [Chemical 6]

【００３８】また、ポリシラザン変性物として、例えば
下記の構造（式中、側鎖の金属原子であるＭは架橋をな
していてもよい）のように金属原子を含むポリメタロシ
ラザンも出発材料として用いることができる。As the modified polysilazane, for example, a polymetallosilazane containing a metal atom as shown in the following structure (wherein the metal atom M of the side chain may be crosslinked) is also used as a starting material. be able to.

【００３９】[0039]

【化７】 [Chemical 7]

【００４０】その他、繰り返し単位が〔（ＳｉＨ2）n
（ＮＨ）m〕および〔（ＳｉＨ2）rＯ〕（これら式中、
ｎ、ｍ、ｒはそれぞれ１、２または３である）で表され
るポリシロキサザン（特開昭６２−１９５０２４号公
報）、ポリシラザンにボロン化合物を反応させて製造す
る耐熱性に優れたポリボロシラザン（特開平２−８４４
３７号公報）、ポリシラザンとメタルアルコキシドとを
反応させて製造するポリメタロシラザン（特開昭６３−
８１１２２号、同６３−１９１８３２号、特開平２−７
７４２７号各公報）、分子量を増加させたり、耐加水分
解性を向上させた無機シラザン高重合体や改質ポリシラ
ザン（特開平１−１３８１０８号、同１−１３８１０７
号、同１−２０３４２９号、同１−２０３４３０号、同
４−６３８３３号、同３−３２０１６７号公報）、ポリ
シラザンに有機成分を導入した厚膜化に有利な共重合シ
ラザン（特開平２−１７５７２６号、同５−８６２００
号、同５−３３１２９３号、同３−３１３２６号公
報）、ポリシラザンにセラミックス化を促進するための
触媒的化合物を付加または添加したプラスチックスやア
ルミニウムなどの金属への施工が可能で、より低温でセ
ラミックス化する低温セラミックス化ポリシラザン（特
開平５−２３８８２７号、同６−１２２８５２号、同６
−２９９１１８号、同６−３０６３２９号、同６−２４
０２０８号、同７−１９６９８６号公報）などが挙げら
れる。In addition, the repeating unit is [(SiH 2 ) n
(NH) m ] and [(SiH 2 ) r O] (wherein
n, m, and r are 1, 2 or 3, respectively, and polysiloxazane represented by JP-A-62-195024, polysilazane produced by reacting a boron compound with polysilazane and having excellent heat resistance. Silazane (JP-A-2-844
37), polymetallosilazanes produced by reacting polysilazanes with metal alkoxides (JP-A-63-
81122, 63-191832, JP-A 2-7.
No. 7427), an inorganic silazane high polymer or a modified polysilazane having an increased molecular weight or improved hydrolysis resistance (JP-A-1-138108, 1-138107).
No. 1-203429, No. 1-203430, No. 4-63833, No. 3-320167), and a copolymerized silazane which is advantageous for thickening a film by introducing an organic component into polysilazane (JP-A-2-175726). No. 5-86200
No. 5-331293, No. 3-31326), polysilazane can be applied to a metal such as plastics or aluminum in which a catalytic compound for promoting ceramization is added or added at a lower temperature. Low temperature ceramized polysilazane to be ceramized (JP-A-5-238827, 6-122852, 6)
-299118, 6-306329, 6-24
Nos. 0208 and 7-196986).

【００４１】さらに、ケイ素アルコキシド付加ポリシラ
ザン（特開平５−２３８８２７号公報）、グリシドール
付加ポリシラザン（特開平６−１２２８５２号公報）、
アセチルアセトナト錯体付加ポリシラザン（特開平６−
３０６３２９号公報）、金属カルボン酸塩付加ポリシラ
ザン（特開平６−２９９１１８号、同６−２９９１１８
号公報）のような低温セラミックス化ポリシラザンが挙
げられる。Further, silicon alkoxide-added polysilazane (JP-A-5-238827), glycidol-added polysilazane (JP-A-6-122852),
Acetylacetonato complex-added polysilazane (JP-A-6-
306329), polycarboxylic acid-added polysilazanes (JP-A-6-299118 and 6-299118).
Low temperature ceramized polysilazanes, such as those disclosed in Japanese Patent No.

【００４２】また他のポリシラザンとしては、特開平９
−３１３３３号公報に記載されるような上記のごとき種
々のポリシラザンまたは変性物に、アミン類または／お
よび酸類を添加してなるポリシラザン組成物が挙げられ
る。この組成物がポリシラザンとして用いられる場合に
は、処理溶剤としては、キシレン、アニソール、デカリ
ン、シクロヘキサン、シクロヘキセン、メチルシクロヘ
キサン、エチルシクロヘキサン、リモネン、ヘキサン、
オクタン、ノナン、デカン、Ｃ８−Ｃ１１アルカン混合
物、Ｃ８−Ｃ１１芳香族炭化水素混合物、およびＣ８以
上の芳香族炭化水素を５重量％以上、２５重量％以下含
有する脂肪族／脂環式炭化水素混合物、ジブチルエーテ
ルからなる群から選ばれる１種または二種以上からなる
単一または混合溶剤のいずれも好ましく用いることがで
きる。Another polysilazane is disclosed in Japanese Patent Application Laid-Open No. 9-29138.
There are mentioned polysilazane compositions obtained by adding amines and / or acids to the above-mentioned various polysilazanes or modified products as described in JP-A-313333. When this composition is used as polysilazane, the treatment solvent is xylene, anisole, decalin, cyclohexane, cyclohexene, methylcyclohexane, ethylcyclohexane, limonene, hexane,
Octane, nonane, decane, C8-C11 alkane mixture, C8-C11 aromatic hydrocarbon mixture, and aliphatic / alicyclic hydrocarbon mixture containing 5 wt% or more and 25 wt% or less of C8 or more aromatic hydrocarbon Any single or mixed solvent consisting of one or two or more selected from the group consisting of dibutyl ether and dibutyl ether can be preferably used.

【００４３】さらに他のポリシラザンとしては、ペルヒ
ドロポリシラザンにメタノールのごときアルコール（特
開平５−３４５８２６号公報）あるいはヘキサメチルジ
シラザン（特開平４−６３８３３号公報）を末端Ｎ原子
に付加して得られた変性ポリシラザンが挙げられる。Still another polysilazane is obtained by adding perhydropolysilazane to an alcohol such as methanol (JP-A-5-345826) or hexamethyldisilazane (JP-A-4-63833) at the terminal N atom. The modified polysilazane thus obtained is mentioned.

【００４４】本発明の溶剤が適用されるポリシラザンの
形態は、被膜状のものであることが通常であるが、被膜
状のものに限られるものではない。また、ポリシラザン
を基材上に被覆する方法としては、例えばスピンコー
ト、スプレーコート、フローコート、ローラーコート、
ディップコート、布拭き法、スポンジ拭き法等従来知ら
れた方法のうち何れの方法であってもよく、何ら限定さ
れるものではない。また基材の形状も板状、フィルム状
などいずれの形状でもよく、表面状態も平坦でも凹凸状
であっても、曲面であってもよい。基材の材質も半導
体、ガラス、金属、金属酸化物、プラスチックなどいず
れのものでもよい。The form of polysilazane to which the solvent of the present invention is applied is usually in the form of a film, but is not limited to the form of a film. Further, as a method of coating the polysilazane on the substrate, for example, spin coating, spray coating, flow coating, roller coating,
Any of conventionally known methods such as a dip coating method, a cloth wiping method, and a sponge wiping method may be used without any limitation. Further, the shape of the base material may be any shape such as a plate shape or a film shape, and the surface condition may be flat, uneven or curved. The material of the base material may be any of semiconductor, glass, metal, metal oxide, plastic and the like.

【００４５】また、本発明の溶剤をポリシラザンと接触
させる方法も何等限定されるものではなく、基材上のポ
リシラザンへのノズルからの溶剤の噴射あるいは噴霧、
ポリシラザンが被覆された基材の溶剤中への浸漬、溶剤
によるポリシラザンの洗い流しなど任意の方法であって
よい。The method of contacting the solvent of the present invention with polysilazane is not limited in any way, and the solvent may be sprayed or sprayed from a nozzle onto polysilazane on the substrate.
Any method may be used, such as immersing the substrate coated with polysilazane in a solvent, washing the polysilazane with the solvent, or the like.

【００４６】例えば、半導体基板（シリコンウエハ）に
ポリシラザン溶液を被覆し、半導体基板上に層間絶縁
膜、平坦化膜、パシベーション膜あるいは素子間分離膜
などを形成する場合を例として、本発明の溶剤をポリシ
ラザンと接触させる方法を説明すると、スピンコーター
に、必要に応じ半導体、配線などが形成された４インチ
シリコンウエハを取り付け、例えば５００〜４０００ｒ
ｐｍの回転速度で回転するウエハにポリシラザン溶液を
スピンコート法により塗布し、次いでこのポリシラザン
が塗布されたウエハを例えば５００〜４０００ｒｐｍの
回転速度で回転させた状態でエッジ部および背面にノズ
ルから本発明の溶剤を洗浄液（リンス液）として噴射す
ることにより、溶剤とポリシラザンの接触が図られ、ウ
エハのエッジ部のビードの除去、平坦化および裏面に周
り込んだポリシラザン塗膜の除去がなされる。For example, the case where a semiconductor substrate (silicon wafer) is coated with a polysilazane solution and an interlayer insulating film, a planarizing film, a passivation film or an element isolation film is formed on the semiconductor substrate is taken as an example, and the solvent of the present invention is used. The method of contacting the polysilazane with polysilazane will be described. A 4-inch silicon wafer on which a semiconductor, wiring and the like are formed, if necessary, is attached to a spin coater, and the spin coater is, for example, 500 to 4000r.
The present invention applies a polysilazane solution to a wafer rotating at a rotation speed of pm by a spin coating method, and then applies the wafer coated with the polysilazane to the edge portion and the back surface from a nozzle while rotating the wafer at a rotation speed of, for example, 500 to 4000 rpm. By spraying the solvent as a cleaning liquid (rinsing liquid), the solvent and the polysilazane are brought into contact with each other, so that the bead at the edge portion of the wafer is removed, the surface is flattened, and the polysilazane coating film around the back surface is removed.

【００４７】[0047]

【実施例】以下、実施例により本発明を具体的に説明す
るが、これら実施例によって本発明が何等の限定をうけ
るものではない。なお、以下の実施例においては、参考
例１〜３に記載されるポリシラザンが用いられた。EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In addition, in the following examples, the polysilazanes described in Reference Examples 1 to 3 were used.

【００４８】参考例１（ペルヒドロポリシラザンの合
成） 内容積３００ｍｌの四つ口フラスコにガス吹き込み管、
メカニカルスターラー、ジュワーコンデンサーを装着し
た。反応器内部を脱酸素した乾燥窒素で置換した後、四
つ口フラスコに脱気した乾燥ピリジン１５０ｍｌを入
れ、これを氷冷した。次に、ジクロロシラン１６．１ｇ
を５０分間かけて加えたところ、白色固体状のアダクツ
（ＳｉＨ2Ｃｌ2・２Ｐｙ）が生成した。反応混合物を氷
冷し、激しく攪拌しながら、ソーダライム管および活性
炭管を通して精製したアンモニア１０．９ｇを窒素ガス
と混合して、１時間かけて吹き込んだ。反応終了後、固
体生成物を遠心分離した後、更に濾過して除去した。濾
液から溶媒を減圧除去（５０℃、５ｍｍＨｇ、２時間）
することにより、ガラス状固体ポリシラザン５．５２ｇ
を得た。蒸気圧降下法による分子量は２０００であっ
た。収率は７７％であった。Reference Example 1 (Synthesis of perhydropolysilazane) A four-necked flask having an inner volume of 300 ml was charged with a gas blowing tube,
Equipped with mechanical stirrer and dewar condenser. After replacing the inside of the reactor with deoxygenated dry nitrogen, 150 ml of degassed dry pyridine was put into a four-necked flask, and this was ice-cooled. Next, 16.1 g of dichlorosilane
Was added over 50 minutes, adducts (SiH 2 Cl 2 · 2Py) in the form of white solid were produced. The reaction mixture was ice-cooled and, with vigorous stirring, 10.9 g of purified ammonia was mixed with nitrogen gas through a soda lime tube and an activated carbon tube, and the mixture was blown in over 1 hour. After the reaction was completed, the solid product was separated by centrifugation and then filtered. Removal of solvent from the filtrate under reduced pressure (50 ° C, 5 mmHg, 2 hours)
By doing, 5.52 g of glassy solid polysilazane
Got The molecular weight measured by the vapor pressure reduction method was 2000. The yield was 77%.

【００４９】参考例２（メタノール付加ペルヒドロポリ
シラザンの合成） 特開平５−３４５８２６号公報の実施例１にしたがっ
て、メタノール付加ペルヒドロポリシラザンを合成し
た。得られたメタノール付加ペルヒドロポリシラザンは
以下のような構造を含む。Reference Example 2 (Synthesis of methanol-added perhydropolysilazane) Methanol-added perhydropolysilazane was synthesized according to Example 1 of JP-A-5-345826. The resulting methanol-added perhydropolysilazane has the following structure.

【００５０】[0050]

【化８】 [Chemical 8]

【００５１】参考例３（ヘキサメチルジシラザン付加ペ
ルヒドロポリシラザンの合成） 特開平４−６３８３３号公報の実施例１にしたがって、
ヘキサメチルジシラン付加ペルヒドロポリシラザンを合
成した。得られたヘキサメチルジシラン付加ペルヒドロ
ポリシラザンは以下のような構造を含む。Reference Example 3 (Synthesis of Hexamethyldisilazane-added Perhydropolysilazane) In accordance with Example 1 of JP-A-4-63833.
Hexamethyldisilane-added perhydropolysilazane was synthesized. The resulting hexamethyldisilane-added perhydropolysilazane has the following structure.

【００５２】[0052]

【化９】 [Chemical 9]

【００５３】実施例１〜１５および比較例１〜３ 参考例１で得られたペルヒドロポリシラザンに対し、表
１に記載される各洗浄剤を用いて、ペルヒドロポリシラ
ザンのゲル化日数、発生ガス量およびエッジカット特性
を各々以下の方法により評価した。結果を表２に示す。Examples 1 to 15 and Comparative Examples 1 to 3 The perhydropolysilazane obtained in Reference Example 1 was treated with each of the detergents listed in Table 1 to give the number of gelling days of the perhydropolysilazane and the generated gas. The amount and the edge cut property were evaluated by the following methods. The results are shown in Table 2.

【００５４】（ゲル化日数評価方法）１００ｇのガラス
瓶にペルヒドロポリシラザンのジｎ−ブチルエーテル２
０重量％溶液５ｇと洗浄剤５０ｇを入れて混合し、蓋を
開けた状態で２２℃、５０％ＲＨの室内に放置し、ゲル
化するまでの日数を目視にて観察した。(Evaluation method for gelation days) A 100 g glass bottle was charged with di-n-butyl ether of perhydropolysilazane 2
5 g of a 0 wt% solution and 50 g of a detergent were added and mixed, and the mixture was left in a room at 22 ° C. and 50% RH with the lid open, and the number of days until gelation was visually observed.

【００５５】（発生ガス量の評価方法）１００ｇのガラ
ス瓶にペルヒドロポリシラザンのジｎ−ブチルエーテル
２０重量％溶液５ｇと洗浄剤５０ｇを入れて混合した後
密閉し、１時間後に気相部分をサンプリングしてガスク
ロマトグラフにて測定した。(Evaluation Method of Amount of Evolved Gas) In a 100 g glass bottle, 5 g of a 20% by weight solution of perhydropolysilazane in di-n-butyl ether and 50 g of a cleaning agent were placed and mixed, and after 1 hour, a gas phase portion was sampled. It was measured with a gas chromatograph.

【００５６】（エッジカット特性の評価方法） 東京エレクトロン社製クリ−ントラックＭａｒｋ−８を
使用して、参考例１で得られたペルヒドロポリシラザン
のジｎ−ブチルエーテル２０重量％溶液を回転数１００
０ｒｐｍで１０秒間スピンコートし、引き続いて洗浄液
を成膜面および裏面に回転数２０００ｒｐｍで５秒間噴
射してウエハのリンスを行い、ペルヒドロポリシラザン
の剥離性（エッジカット特性）を倍率１００倍の光学顕
微鏡で観察した。洗浄液の成膜面および裏面への噴射
は、いずれもウエハ外周面より３ｍｍ内部に行った。(Evaluation Method of Edge-Cut Characteristics) Using a clean track Mark-8 manufactured by Tokyo Electron Co., a 20% by weight solution of di-n-butyl ether of perhydropolysilazane obtained in Reference Example 1 was rotated at 100 rpm.
Spin coating is performed at 0 rpm for 10 seconds, and then a cleaning solution is sprayed on the film formation surface and the back surface at a rotation speed of 2000 rpm for 5 seconds to rinse the wafer, and the peeling property (edge-cutting property) of perhydropolysilazane is magnified 100 times. It was observed under a microscope. Morphism injection to the deposition surface and the back surface of the washing liquid were all performed 3mm inside from the wafer outer peripheral surface.

【００５７】[0057]

【表１】 [Table 1]

【００５８】[0058]

【表２】 [Table 2]

【００５９】実施例１６〜３０および比較例４〜６ 参考例２で得られたメタノール付加ペルヒドロポリシラ
ザンに対し、表３に記載される各洗浄剤を用いて、該ペ
ルヒドロポリシラザンのゲル化日数、発生ガス量および
エッジカット特性を実施例１と同様の方法により評価し
た。結果を表４に示す。Examples 16 to 30 and Comparative Examples 4 to 6 The methanol-added perhydropolysilazane obtained in Reference Example 2 was treated with each of the detergents listed in Table 3, and the gelation days of the perhydropolysilazane were measured. The amount of generated gas and the edge cut property were evaluated in the same manner as in Example 1. The results are shown in Table 4.

【００６０】[0060]

【表３】 [Table 3]

【００６１】[0061]

【表４】 [Table 4]

【００６２】実施例３０〜５５および比較例７〜９ 参考例３で得られたヘキサメチルジシラザン付加ペルヒ
ドロポリシラザンに対し、表５に記載される各洗浄剤を
用いて、該ペルヒドロポリシラザンのゲル化日数、発生
ガス量およびエッジカット特性を実施例１と同様の方法
により評価した。結果を表６に示す。Examples 30 to 55 and Comparative Examples 7 to 9 Hexamethyldisilazane-added perhydropolysilazanes obtained in Reference Example 3 were treated with the respective detergents shown in Table 5 to give the perhydropolysilazanes. The number of gelation days, the amount of generated gas, and the edge cut property were evaluated by the same method as in Example 1. The results are shown in Table 6.

【００６３】[0063]

【表５】 [Table 5]

【００６４】[0064]

【表６】 [Table 6]

【００６５】[0065]

【効果】以上述べたように、本発明の溶剤は、ポリシラ
ザンに対する溶解性、エッジカット特性に優れ、下地と
なる半導体あるいは基板などへの悪影響がなく、また残
留部のポリシラザン塗膜の特性に影響を与えることがな
いため、ポリシラザン処理用溶剤として適している。ま
た本発明の溶剤は、ポリシラザンを分解する基を含ま
ず、また水分含有量が極めて低いため、廃液ラインの詰
まりが防止でき、スピンコーターなどの塗布装置ならび
に廃液ラインの洗浄作業の回数を減らすなど清掃作業の
軽減が図れ、さらに廃液タンク中におけるシランなどの
ガスの発生量を減少させることができ安全性にも優れて
いる。また溶剤中に芳香族系溶剤を含まない場合は人体
に対する安全性に優れたポリシラザン処理溶剤を提供す
ることができる。さらに、この溶剤を使用してポリシラ
ザンを処理することにより、溶剤の使用量が少なく、基
材の特性、残留被膜への影響が少なく、安全で、安価な
ポリシラザンの処理方法を提供することができる。[Effect] As described above, the solvent of the present invention has excellent solubility in polysilazane and edge-cutting properties, has no adverse effect on the underlying semiconductor or substrate, and has an effect on the properties of the polysilazane coating film in the residual portion. Therefore, it is suitable as a solvent for polysilazane treatment. Further, the solvent of the present invention does not contain a group capable of decomposing polysilazane, and has a very low water content, so that clogging of the waste liquid line can be prevented, and the number of times of cleaning operations of a coating device such as a spin coater and the waste liquid line can be reduced. Hakare alleviation of the cleaning operation, and further excellent in our Keru amount of gas generated can be reduced safety such as silane in the waste tank. Further, when the solvent does not contain an aromatic solvent, it is possible to provide a polysilazane treatment solvent which is excellent in safety for the human body. Further, by treating the polysilazane using this solvent, the amount of the solvent used is small, the characteristics of the substrate, the influence on the residual film is small, and it is possible to provide a safe and inexpensive treatment method for polysilazane. .

フロントページの続き (72)発明者 鈴木 直 東京都文京区本駒込二丁目28番８号 文 京グリーンコート センターオフィス９ 階 クラリアント ジャパン 株式会社 内 (56)参考文献 特開 平11−105185（ＪＰ，Ａ) 特開 平10−194873（ＪＰ，Ａ) 特開 平10−194719（ＪＰ，Ａ) 特開 平10−98036（ＪＰ，Ａ) 特開 平８−34957（ＪＰ，Ａ) 特開 平５−88373（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01L 21/304,21/306,21/308 H01L 21/316 Front Page Continuation (72) Inventor Nao Suzuki 2-8-8 Honkomagome, Bunkyo-ku, Tokyo Bunkyo Green Court Center Office, 9th floor, Clariant Japan Co., Ltd. (56) Reference JP-A-11-105185 (JP, A) JP 10-194873 (JP, A) JP 10-194719 (JP, A) JP 10-98036 (JP, A) JP 8-34957 (JP, A) JP 5 -88373 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) H01L 21 / 304,21 / 306,21 / 308 H01L 21/316

Claims (6)

(57)【特許請求の範囲】(57) [Claims] 【請求項１】キシレン、アニソール、デカリン、シクロ
ヘキサン、シクロヘキセン、メチルシクロヘキサン、エ
チルシクロヘキサン、リモネン、ヘキサン、オクタン、
ノナン、デカン、Ｃ８−Ｃ１１アルカン混合物、Ｃ８−
Ｃ１１芳香族炭化水素混合物、Ｃ８以上の芳香族炭化水
素を５重量％以上、２５重量％以下含有する脂肪族／脂
環式炭化水素混合物、およびジブチルエーテルからなる
群から選ばれる一種または二種以上からなる単一または
混合溶剤であって、該溶剤の１ｍｌ中に含まれる０．５
ミクロン以上の微粒子が５０個以下であり、また水分含
有率が１００ｐｐｍ以下であることを特徴とするポリシ
ラザン塗膜または被膜のリンスまたは剥離用処理溶剤。1. Xylene, anisole, decalin, cyclohexane, cyclohexene, methylcyclohexane, ethylcyclohexane, limonene, hexane, octane,
Nonane, decane, C8-C11 alkane mixture, C8-
One or more selected from the group consisting of a C11 aromatic hydrocarbon mixture, an aliphatic / alicyclic hydrocarbon mixture containing 5% by weight or more and 25% by weight or less of a C8 or more aromatic hydrocarbon, and dibutyl ether. A single or mixed solvent consisting of 0.5 contained in 1 ml of the solvent.
There are 50 or less micron-sized particles, and
A treatment solvent for rinsing or peeling a polysilazane coating film or coating, which has a content of 100 ppm or less . 【請求項２】キシレン、Ｃ８−Ｃ１１芳香族炭化水素混
合物またはＣ８以上の芳香族炭化水素を５重量％以上、
２５重量％以下含有する脂肪族／脂環式炭化水素混合物
を５０重量％以上含有する混合溶剤であることを特徴と
する請求項１に記載のポリシラザン塗膜または被膜のリ
ンスまたは剥離用処理溶剤。2. Xylene, C8-C11 aromatic hydrocarbon mixture or C8 or more aromatic hydrocarbon in an amount of 5% by weight or more,
2. The polysilazane coating film or film re-coating according to claim 1, which is a mixed solvent containing 50% by weight or more of an aliphatic / alicyclic hydrocarbon mixture containing 25% by weight or less.
Process solvent for peeling or peeling 【請求項３】さらに希釈溶剤としてミネラルスピリット
が含有されることを特徴とする請求項１または２に記載
のポリシラザン塗膜または被膜のリンスまたは剥離用処
理溶剤。3. A treatment solvent for rinsing or peeling a polysilazane coating film or coating according to claim 1, further comprising mineral spirit as a diluting solvent. 【請求項４】ポリシラザンがペルヒドロポリシラザン、
メタノール付加ペルヒドロポリシラザンまたはヘキサメ
チルジシラザン付加ペルヒドロポリシラザンであること
を特徴とする請求項１〜３のいずれか一項に記載のポリ
シラザン塗膜または被膜のリンスまたは剥離用処理溶
剤。4. The polysilazane is perhydropolysilazane,
Methanol addition perhydropolysilazane or hexamethyldisilazane added claims 1-3 or polysilazane coating film or coating rinsing or stripping process solvent according to one of which is a perhydropolysilazane. 【請求項５】請求項１〜３のいずれか一項に記載の処理
溶剤をポリシラザンと接触させることを特徴とするポリ
シラザン塗膜または被膜のリンスまたは剥離処理方法。5. A method of rinsing or stripping a polysilazane coating film or coating, which comprises contacting the treatment solvent according to any one of claims 1 to 3 with polysilazane. 【請求項６】請求項５に記載のポリシラザン塗膜または
被膜のリンスまたは剥離処理方法において、前記処理溶
剤のポリシラザンとの接触が、ポリシラザン溶液を基板
に塗布した後、前記処理溶剤を基板のポリシラザン塗布
面のエッジ部または裏面に噴射することによりなされる
ことを特徴とするポリシラザン塗膜または被膜のリンス
または剥離処理方法。6. The polysilazane coating film according to claim 5 , or
In the rinsing or release treatment method of the coating, contact with polysilazane of the processing solvent <br/> agents, after applying the polysilazane solution into the substrate, injecting the treating solvent the edge portion or the back of the polysilazane coating surface of the substrate Rinsing of polysilazane coating film or coating characterized by
Or a peeling treatment method.
JP2001396328A 2001-12-27 2001-12-27 Polysilazane treatment solvent and method for treating polysilazane using this solvent Expired - Lifetime JP3479648B2 (en)

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EP02805890.7A EP1463099B1 (en) 2001-12-27 2002-12-19 The use of a solvent for treating polysilazane
PCT/JP2002/013323 WO2003056615A1 (en) 2001-12-27 2002-12-19 Solvent for treating polysilazane and method of treating polysilazane with the solvent
KR1020047010138A KR100859276B1 (en) 2001-12-27 2002-12-19 Solvent for treating polysilazane and method of treating polysilazane with the solvent
US10/499,374 US7344603B2 (en) 2001-12-27 2002-12-19 Solvent for treating polysilazane and method of treating polysilazane with the solvent
CNB028259491A CN100565814C (en) 2001-12-27 2002-12-19 Be used to handle the solvent of polysilazane and adopt this solvent to handle the method for polysilazane
TW091137500A TWI308576B (en) 2001-12-27 2002-12-26 Solvent for treating polysilazane
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